Process for producing resin for paper coating

ABSTRACT

A process for producing a resin is disclosed, comprising reacting (a) a polyalkylenepolyamine, (b) an alicyclic dibasic carboxylic acid and/or a reaction product having a free carboxyl group that is obtained by reacting an alicyclic dibasic carboxylic acid with a glycol, (c) a urea, and (d) an aldehyde and/or an alkylating agent. The resulting resin is useful as a wet strength agent to provide a paper coating composition having improved printability and printing effects.

This is a continuation of application Ser. No. 06,924,020 filed Oct. 28,1986 now abandoned.

FIELD OF THE INVENTION

This invention relates to a process for producing a novel resin usefulfor paper coating, and the like, and to a paper coating compositioncontaining the same, which provides coated paper having excellentprintability and printing effects.

BACKGROUND OF THE INVENTION

Coated paper obtained by applying a paper coating composition mainlycomprising a pigment and an aqueous binder on paper, followed bynecessary steps, such as drying, calendering, etc., has conventionallybeen employed widely for commercial prints, magazines, books, and so onowing to its properties, such as excellent printing effects. With anincreasing demand for higher quality and a development of high-speedprinting techniques, constant efforts have been made to improve thequality of coated paper. In particular, in the field of offset printingthat is in a majority among various printing techniques, it is a weightysubject to improve ink receptivity and water resistance, e.g., wet pickor wet rub, under the influence of wetting water, and anti-blisterproperty on a rotary press.

A conventional approach to the above-described subject is addition ofwet strength agents and the like, such as a melamine-formaldehyde resin,a urea-formaldehyde resin, a polyamidepolyurea-formaldehyde resin, apolyamidepolyurea-formaldehyde-epihalohydrin resin, and those disclosedin Japanese Patent Publication Nos. 11667/69 and 32597/84, JapanesePatent Application (OPI) NO. 40322/83, etc. (the term "OPI" as usedherein means "unexamined published application").

These wet strength agents and the like, though exhibiting the respectiveeffects, are not satisfactory for practical use due to seriousdisadvantages. For example, aminoplast resins includingmelamine-formaldehyde resins, urea-formaldehyde resins, etc. not onlycause considerable evolution of formaldehyde from coated paper duringworking but also virtually fail to achieve improvements in inkreceptivity or anti-blister property. Moreover, the expected effect toimprove water resistance becomes hard to obtain as a pH of a papercoating composition increases. Although thepolyamidepolyurea-formaldehyde resin is effective on improvement ofwater resistance as well as ink receptivity and anti-blister property,the degree of reached improvement is still insufficient for satisfyingrecent requirements for higher coated paper qualities. Therefore, thereis much room for further improvement of performances.

SUMMARY OF THE INVENTION

An object of this invention is to provide a process for producing anovel resin, by which high water resistance, ink receptivity, and thelike that cannot be achieved by the conventional techniques can beimparted to coated paper.

Another object of this invention is to provide a paper coatingcomposition containing such a resin, which can produce coated paperhaving high water resistance, ink receptivity, and the like.

As a result of extensive investigations with the above objects, theinventors have now found a process for obtaining a resin that meets theabove-described requirements and also proved that a paper coatingcomposition comprising (1) a pigment, (2) an aqueous binder and (3) theabove resin is extremely effective for accomplishing the above objects.

The present invention provides a process for producing a resin, whichcomprises reacting (a) a polyalkylenepolyamine, (b) an alicyclic dibasiccarboxylic acid and/or a reaction product having a free carboxyl groupthat is obtained by the reaction between an alicylic dibasic carboxylicacid and a glycol, (c) a urea, and (d) an aldehyde and/or an alkylatingagent.

The present invention further relates to a paper coating compositioncomprising (1) a pigment, (2) an aqueous binder, and (3) the resinobtained by the above-described process.

A chief feature of this invention consists in the use of the component(b), i.e., an alicyclic dibasic carboxylic acid and/or a reactionproduct having a free carboxyl group obtained by the reaction between analicylic dibasic carboxylic acid and a glycol. The resin obtained by thepresent invention has marked improvements in performances over theconventionally employed paper coating resins obtained from aliphatic oraromatic dibasic carboxylic acids.

DETAILED DESCRIPTION OF THE INVENTION

The polyalkylenepolyamines (a) which can be used in the invention arecompounds containing two primary amino groups and at least one secondaryamino group per molecule. Specific examples of such compounds includediethylenetriamine, triethylenetetramine, tetraethylenepentamine,iminobispropylamine, 3-azahexane-1,6-diamine,4,7-diazadecane-1,10-diamine, etc. These polyalkylenepolyamines can beused either individually or as mixtures of two or more thereof. It ispossible to use aliphatic diamines, e.g., ethylenediamine,propylene-diamine, dimethylaminopropylamine, etc., heterocyclicpolyamines, e.g., bisaminomethylpiperazine, aminoethylpiperazine, etc.,and the like in combination with the above-describedpolyalkylenepolyamines as far as such a combined use does not deviatefrom the purpose of this invention.

The alicylic dibasic carboxylic acids (b) are compounds having twocarboxyl groups per molecule inclusive of esters and anhydrides thereof.Typical examples of such alicylic dibasic carboxylic acids includecarboxylic acids, e.g., tetrahydrophthalic acid, hexahydrophthalic acid,cyclohexane-1,4-dicarboxylic acid, 4-methyltetrahydrophthalic acid,etc., and esters thereof; acid anhydrides, e.g., tetrahydrophthalicanhydride, hexahydrophthalic anhydride, 4-methyltetrahydrophthalicanhydride, 4-methylhexahydrophthalic anhydride, Δ⁴ -tetrahydrophthalicanhydride, 4-methyl Δ⁴ -tetrahydrophthalic anhydride, etc.; and a 1:2adduct of a styrene and maleic anhydride.

These carboxylic acids may be used either individually or in combinationthereof. Unless hindering the effects of the invention, other dibasiccarboxylic acids, such as aliphatic dicarboxylic acids (e.g., adipicacid, glutaric acid, etc.) or aromatic dicarboxylic acids (e.g.,terephthalic acid, phthalic acid, etc.), may be used in combination withthese alicyclic dibasic carboxylic acids.

Examples of the glycols which can be used in the present inventioninclude alkylene glycols, e.g., ethylene glycol, propylene glycol,butanediol, etc., cycloalkylene glycols, e.g., cyclopentanediol,cyclohexanediol, etc., alkenylene glycols, e.g., butenediol, octenediol,etc., polyalkylene glycols, e.g., diethylene glycol, dipropylene glycol,triethylene glycol, polyethylene glycol, polytetramethylene glycol,etc., ethylene oxide adducts of bisphenol A, ethylene oxide adducts ofhydrogenated bisphenol A, and the like.

The reaction product having a free carboxyl group which is obtained byreacting an alicyclic dibasic carboxylic acid and a glycol is acarboxyl-terminated polyester obtained by reacting the above-recitedalicyclic dibasic carboxylic acid and the above-recited glycol at amolar ratio of excess carboxylic acid. This reaction is usually carriedout in the presence or absence of a catalyst at a temperature of from80° to 200° C. for a period of from 30 minutes to 2 hours.

The ureas (c) specifically include urea, thiourea, guanylurea,methylurea, dimethylurea, etc., with urea being preferred from anindustrial viewpoint.

The aldehydes (d) include monoaldehydes, e.g., formaldehyde,acetaldehyde, propionaldehyde, acrolein, glyoxylic acid, glycolaldehyde,etc., and polyaldehydes, e.g., glyoxal, glutaraldehyde, etc. Of these,the preferred monoaldehyde is formaldehyde, and the preferredpolyaldehyde is glyoxal.

The alkylating agent to be used as component (d) includes the followingcompounds (i) to (vi):

(i) Halogen-containing compounds represented by formula

    R.sub.1 ---X

wherein R₁ represents a lower alkyl group, an alkenyl group, a benzylgroup or a phenoxyethyl group; and X represents a halogen atom.Preferred examples are methyl chloride, ethyl chloride, propyl chloride,allyl chloride, benzyl chloride, phenoxyethyl chloride, andcorresponding bromides and iodides.

(ii) Dialkyl sulfites and dialkyl sulfates represented by formula:

    (R.sub.2 O).sub.2 SO.sub.v

wherein R₂ represents a lower alkyl group; and v represents 1 or 2.

Preferred examples are dimethyl sulfate, diethyl sulfate, dimethylsulfite, diethyl sulfite, etc.

(iii) Ethylene oxide derivatives represented by formula: ##STR1##wherein R₃ represents a hydrogen atom, a lower alkyl group, ahydroxyalkyl group or a phenyl group. Preferred examples are ethyleneoxide, propylene oxide, butylene oxide, styrene oxide, glycidol, etc.

(iv) Epihalohydrins represented by formula: ##STR2## wherein Xrepresents a halogen atom; and w represents 1, 2 or 3.

Preferred examples are epichlorohydrin, epibromohydrin, etc.

(v) Monohalohydrins represented by formula:

    HOCH.sub.2 (CH.sub.2).sub.w X

wherein X and w are as defined above.

Preferred examples are ethylene chlorohydrin, ethylene bromohydrin, etc.

(vi) Dihalohydrins represented by formula: ##STR3## wherein X is asdefined above; and either one of Y and Z represents a halogen atom, withthe another being a hydroxyl group. Preferred examples are1,3-dichloro-2-propanol, 2,3-dichloro-1-propanol, etc.

The preferred among these alkylating agents is epichlorohydrin. Theabove-described compounds may be used individually or in combinations oftwo or more thereof.

Not only either aldehydes or alkylating agents but the both may be usedas component (d) on condition that the aldehyde to be used incombination with the alkylating agent is selected from formaldehyde,glyoxal and a mixture thereof

The process for producing the resin according to the present inventionwill be described. The resin can be prepared by, for example, reacting areaction product of components (a), (b) and (c) with component (d). Theorder for reacting components (a), (b) and (c) can be selectedarbitrarily.

For example, components (a) and (b) are first reacted, and then theresulting product is reacted with component (c). The reaction betweencomponents (a) and (b) can be effected at a temperature of from 120° to250° C., and preferably from 130° to 200° C., for a period of from 2 to12 hours while driving produced water out of the system. From 0.4 to 4equivalents, and preferably from 0.8 to 3 equivalents, of carboxylgroups in component (b) is reacted per mol of component (a),polyalkylenepolyamines. The subsequent reaction between the resultingdehydration condensation product and component (c), ureas, can becarried out at a temperature ranging from 100° to 180° C., andpreferably from 110° to 160° C., for a period of from 1 to 6 hours whileremoving produced ammonia out of the system. The amount of component (c)to be used is not more than 1 equivalent, and preferably from 0.1 to 0.8equivalent, per equivalent of the amino groups in component (a), i.e.,primary and secondary amino groups.

Another procedure for reaction comprises first reacting components (a)and (c), then reacting the product with component (b), and furtherreacting the resulting product with component (c). The first reaction isconducted at a temperature of from 100° to 180° C., and preferably from110° to 160° C., for a period of from 1 to 6 hours to remove ammonia.The amount of component (c) to be used is from 0.2 to 1 mol, andpreferably from 0.3 to 0.8 mol, per mol of component (a). The resultingreaction product is then reacted with component (b) at a temperature offrom 120° to 250° C., and preferably from 130° to 200° C., for a periodof from 2 to 12 hours while removing produced water out of the system.The component (b) is used in an amount of from 0.2 to 2 equivalents, andpreferably from 0.3 to 1.8 equivalents, per mol of component (a). Thefinal reaction between the reaction product of components (a), (b) and(c) and component (c) can be performed at a temperature of from 100° to180° C., and preferably from 110° to 160° C., for a period of from 1 to6 hours. The amount of component (c) to be used here is not more than 2equivalents, and preferably in a range of from 0.1 to 1.5 equivalent,per equivalent of secondary amino groups in component (a).

A still another procedure for reaction comprises simultaneously reactingcomponents (a), (b) and (c), and then further reacting the resultingproduct with component (c). The first reaction of components (a), (b)and (c) can be achieved at a temperature of from 100° to 200° C., andpreferably from 110° to 180° C., for a period of from 2 to 12 hourswhile removing produced ammonia and water out of the reaction system. Asuitable ratio of components (a), (b) and (c) in this reaction step isfrom 0.2 to 2 equivalents, and preferably from 0.3 to 1.8 equivalents,of carboxyl groups in component (b) and from 0.2 to 1 mol, andpreferably from 0.3 to 0.8 mol, of component (c), per mol of component(a). The resulting reaction product is then reacted with component (c)at a temperature of from 100° to 180° C., and preferably from 110° to160° C., for a period of from 1 to 6 hours. The amount of component (c)to be suitably used in this reaction is not more than 2 equivalents, andpreferably from 0.1 to 1.5 equivalents, per equivalent of secondaryamino groups in component (a).

The reaction product of components (a), (b) and (c) as obtained by anyof these reaction procedures is dissolved in water and then reacted withcomponent (d), i.e., aldehydes and/or alkylating agents.

The reaction with aldehydes alone can be carried out in an aqueoussolution at a concentration of from 20 to 70%, and preferably from 30 to60%, by weight at a temperature of from 40° to 80° C. for a period offrom 1 to 10 hours. The amount of the polyaldehydes or monoaldehydes tobe used is from 0.05 to 1.0 mol, and preferably from 0.1 to 0.8 mol, orfrom 0.1 to 1.0 mol, and preferably from 0.2 to 0.7 mol, respectively,per mol of component (c). After completion of the reaction, the reactionmixture is adjusted, if necessary, to a pH of from 4 to 7 by addition ofan alkali, e.g., sodium hydroxide, potassium hydroxide, etc., or anacid, e.g., hydrochloric acid, sulfuric acid, etc.

The reaction with alkylating agents can be conducted in an aqueoussolution at a concentration of from 20 to 80%, and preferably from 30 to70%, by weight, and a pH ranging from 3 to 12 at a reaction temperatureof from 20° to 80° C. for a period of from 1 to 10 hours. A suitableamount of the alkylating agents to be used is not more than 2equivalents, and preferably from 0.1 to 1.5 equivalents, per equivalentof secondary amino groups in component (a).

If in using both aldehydes an alkylating agents as component (d), theorder of reacting the reaction product of components (a), (b) and (c)with these compounds is arbitrarily selected. That is, the objects ofthe present invention can be accomplished through any of the reactionwith aldehydes followed by the reaction with alkylating agents; thereaction with alkylating agents followed by the reaction with aldehydes;and the simultaneous reaction with aldehydes and alkylating agents.

When formaldehyde and/or glyoxal as aldehydes and the alkylating agentsare both employed, the amount of the former is not more than 1 mol, andpreferably from 0.1 to 0.8 mol, per mol of component (c); and that ofthe latter is not more than 2 equivalents, and preferably from 0.1 to1.5 equivalents, per equivalent of secondary amino groups of component(a). The reaction system preferably has a pH of from 5 to 8 in the caseof using glyoxal, and of from 3 to 7 in the case of using formaldehyde.If necessary, the system after completion of the reaction is adjusted toa pH of from 4 to 8 with an alkali, e.g., sodium hydroxide, potassiumhydroxide, etc., or an acid, e.g., hydrochloric acid, sulfuric acid,formic acid, etc.

The thus obtained resin is useful as component (3) of the paper coatingcomposition according to the present invention.

The pigments which can be used as component (1) of the paper coatingcomposition of the invention are selected from white inorganic pigments,such as kaolin, talc, calcium carbonate (either ground or precipitated),aluminum hydroxide, satin white, titanium dioxide, etc.; white organicsynthetic pigments, such as polystyrene, melamine-formaldehyde resins,urea-formaldehyde resins, etc.; and mixtures of two or more thereof. Inaddition, inorganic or organic color pigments may also be used incombination.

The aqueous binders as component (2) include water-soluble binders, suchas phosphate-esterified starch, oxidized starch, polyvinyl alcohol,casein, gelatin, carboxymethyl cellulose, etc.; aqueous emulsion typebinders, such as styrene-butadine resins, vinyl acetate resins,ethylene-vinyl acetate resins, methyl methacrylate-butadiene resins,etc.; and mixtures of two or more thereof.

The paper coating composition according to the present inventioncomprises from 1 to 50 parts, and preferably from 6 to 40 parts, byweight of the aqueous binder (2) and from 0.05 to 10 parts, andpreferably from 0.1 to 3 parts, by weight of the resin (3) per 100 partsby weight of the pigment (1), with the solids content ranging from 20 to75% by weight based on the composition.

In the preparation of the paper coating composition, the resin (3) isusually added to the pigment and aqueous binder. The same results can beobtained if the resin is previously added to a pigment slurry and/or anaqueous binder.

The coating composition according to this invention can further contain,if desired, various additives, such as dispersing agents, viscocisty-and fluidity-controlling agents, defoaming agents, anti-septics,lubricants, water retaining agents, colorants including dyes and coloredpigments, and the like.

The order of compounding the above-described components is notparticularly limited However, in compounding, it is desirable toappropriately select the order of compounding, the solids content ofeach component to be compounded, the pH level of the resultingcomposition so as to prevent reduction in dispersion stability of thecomposition due to differences in inoic characteristics.

The paper coating composition of the invention is applied on a paperbase by any of commonly employed coating methods, such as blade coating,air knife coating, roll coating, side roll coating, gate roll coating,cast coating, and the like, followed by drying as required in a usualmanner. If desired, the coated paper is supercalendered

The coated paper thus obtained by the use of the paper coatingcomposition in accordance with the present invention possesses variousexcellent performances, such as high ink receptivity, high waterresistance, improved surface gloss, improved opacity, improvedanti-blister property, freedom from a formaldehyde odor, and the like.

The term "paper" in "paper coating composition" has been used in itsbroadest sense and includes paper and paperboard in the narrow sense.

This invention will now be illustrated in greater detail with referenceto the following examples, but it should be understood that they are notintended to limit the present invention. In these examples, all theparts and percents are given by weight unless otherwise indicated.

EXAMPLE 1

In a four-necked flask equipped with a thermometer, a reflux condenserand a stirrer were charged 58.5 parts (0.4 mol) of triethylenetetramineand 12.0 parts (0.2 mol) of urea, and the mixture was heated at an innertemperature of 120° to 140° C. for 3 hours to effect deammoniation.Then, 34.4 parts (0.2 mol) of hexahydrophthalic acid was added thereto,and the mixture was heated at 150° to 160° C. for 5 hours to effectdehydrating amidation. After cooling to 130° C., 48.0 parts (0.8 mol) ofurea was added to the reaction mixture, and the mixture was heated at120° to 130° C. for 2 hours to perform deammoniation. After cooling to100° C., water was added to make a 50% aqueous solution. To the reactionmixture was added 58 parts (0.4 mol) of 40% glyoxal, and the mixture wasadjusted to a pH of 6 with 35% hydrochloric acid, followed by reactingat 50° C. for 3 hours. After completion of the reaction, the reactionmixture was cooled to 25° C. to obtain a resin solution R₁ having aconcentration of 47% and a viscosity of 46 cp (at 25° C.; hereinafterthe same).

EXAMPLE 2

In the same vessel as used in Example 1, 58.5 parts (0.4 mol) oftriethylenetetramine and 12.0 parts (0.2 mol) of urea were charged andheated at an inner temperature of 120° to 140° C. for 3 hours to effectdeammoniation. Thereafter, 33.2 parts (0.2 mol) of HN-2200 (a trade nameof an alicyclic acid anhydride of formula: ##STR4## produced by HitachiChemical Co., Ltd.) was added to the reaction mixture, followed byheating at an inner temperature of 150° to 160° C. for 5 hours to effectdehydrating amidation. After lowering the inner temperature to 130° C.,12.0 parts (0.2 mol) of urea was charged, and the mixture was heated at120° to 130° C. for 2 hours for deammoniation, followed by cooling to100° C. Water was added to the reaction mixture to make a 50% aqueoussolution.

To the aqueous solution was added 29 parts (0.2 mol) of 40% glyoxal, andthe pH was adjusted to 6.5 with 70% sulfuric acid. The mixture washeated up to 60° C., at which temperature the reaction was continued for4 hours. The reaction mixture was cooled to 25° C. to obtain a resinsolution R2 having a concentration of 48.5% and a viscosity of 47 cp.

EXAMPLE 3

In the same vessel as used in Example 1, 58.5 parts (0.4 mol) oftriethylenetetramine, 30.4 parts of tetrahydrophthalic anhydride and 12parts (0.2 mol) of urea were charged simultaneously. The mixture washeated at 150° to 155° C. for 5 hours to simultaneously performdehydrating amidation and deammoniation. After cooling to 130° C., 12parts (0.2 mol) of urea was additionally charged, followed by heating at125° to 130° C. for 2 hours to conduct deammoniation. The reactionmixture was diluted with water to make a 50% aqueous solution.

To the resulting solution was added 80 parts (0.2 mol) of a 25% aqueoussolution of glutaraldehyde. After adjusting to a pH of 6.5 with 70%sulfuric acid, the mixture was allowed to react at 55° C. for 7 days,followed by cooling to 25° C. to obtain a resin solution R3 having aconcentration of 45% and a viscosity of 42 cp.

EXAMPLE 4

In the same vessel as in Example 1 was charged 29.2 parts (0.2 mol) oftriethylenetetramine, and 30.8 parts (0.2 mol) of hexahydrophthalicanhydride was added thereto. The mixture was heated at 150° to 155° C.for dehydrating amidation. After the reaction mixture was cooled to 130°C., 12 parts (0.2 mol) of urea was added thereto, followed by heating at125° to 130° C. for 2 hours to effect deammoniation. The reactionmixture was cooled to 60° C. and diluted with water to make a 50%aqueous solution.

Then, 14.5 parts (0.1 mol) of 40% glyoxal was added thereto, and themixture was adjusted to a pH of 6 with 35% hydrochloric acid, followedby reacting at 65° C. for 2 hours. After cooling to 25° C., there wasobtained a resin solution R4 having a concentration of 48.5% and aviscosity of 58 cp.

EXAMPLE 5

In the same vessel as in Example 1 were charged 12.4 parts (0.2 mol) ofethylene glycol and 60.8 parts (0.4 mol) of tetrahydrophthalicanhydride, and the mixture was heated at 140° C. for 2 hours to form areaction product having a free carboxyl group. To the reaction mixturewas added 12.0 parts (0.2 mol) of urea, and 58.5 parts (0.4 mol) oftriethylenetetramine was added thereto while stirring at 110° to 120° C.The resulting mixture was subjected to deammoniation and dehydratingamidation by heating at 150° C. for 5 hours. After cooling to 130° C.,an additional 12 parts (0.2 mol) of urea was added thereto, followed byallowing to react at 120° to 130° C. for 2 hours to effectdeammoniation. The reaction mixture was cooled to 100° C., and water wasadded thereto to make a 50% aqueous solution.

Then, 1.45 parts (0.1 mol) of 40% glyoxal was charged therein, and themixture was adjusted to a pH of 7 with 70% sulfuric acid, followed byreacting at 60° C. for 2 hours. The reaction mixture was cooled to 25°C. to obtain a resin solution R5 having a concentration of 49% and aviscosity of 49 cp.

EXAMPLE 6

In the same vessel as in Example 1, 58.5 parts (0.4 mol) oftriethylenetetramine and 12.0 parts (0.2 mol) of urea were charged,followed by heating at an inner temperature of 120° to 140° C. for 3hours to effect deammoniation. Thereafter, 30.4 parts (0.2 mol) oftetrahydrophthalic anhydride was added thereto, and the mixture washeated at an inner temperature of 150° to 160° C. for 5 hours to effectdehydrating amidation. After cooling to an inner temperature of 18° C.,48 parts (0.8 mol) of urea was added, and the mixture was subjected todeammoniation at 120° to 130° C. for 2 hours. After cooling to 100° C.,water was added to the reaction mixture to make a 50% aqueous solution.

Then, 29 parts (0.2 mol) of 40% glyoxal was added to the solution, andthe mixture was adjusted to a pH of 6 with 70% sulfuric acid, followedby reacting at 60° C. for 3 hours. To the reaction mixture was added16.2 parts (0.2 mol) of 37% formalin, and the mixture was adjusted to apH of 5 with 70% sulfuric acid, followed by again reacting at 60° C. for3 hours. After completion of the reaction, the reaction mixture wascooled to 25° C. and adjusted to a pH of 6 with a 28% sodium hydroxideaqueous solution to obtain a resin solution R6 having a concentration of48% and a viscosity of 56 cp.

EXAMPLE 7

In the same vessel as used in Example 1, 58.5 parts (0.4 mol) oftriethylenetetramine and 12 parts (0.2 mol) of urea were charged, andthe mixture was heated at 145° to 150° C. for 4 hours to effectdeammoniation. Separately, 60.8 parts (0.4 mol) of tetrahydrophthalicanhydride and 15.2 parts (0.2 mol) of propylene glycol were mixed andheated at 140° to 150° C. for 2 hours to prepare a polyester. The wholequantity of the resulting polyester was transferred to the abovereaction vessel after completion of deammoniation, and the mixture washeated at an inner temperature of 150° to 155° C. for 4 hours to effectdehydration and deammoniation. After cooling to 130° C., 12 parts (0.2mol) of urea was added thereto, followed by deammoniation at 125° to130° C. for 2 hours. Water was added to the reaction mixture to make a50% aqueous solution, and to the solution were added 40 parts of a 25%aqueous solution of glutaraldehyde and 4 parts (0.05 mol) of 37%formalin. After adjusting to a pH of 5.5 with 70% sulfuric acid, themixture was heated to 70° C., at which temperature the mixture wasallowed to react for 4 hours, followed by cooling to 25° C. Theresulting reaction mixture was adjusted to a pH of 6.5 with a 28% sodiumhydroxide aqueous solution to obtain a resin solution R7 having aconcentration of 47.5% and a viscosity of 46 cp.

COMPARATIVE EXAMPLE 1

A resin solution R8 having a concentration of 47% and a viscosity of 44cp was prepared in the same manner as described in Example 1, except forreplacing the hexahydrophthalic acid with 29.6 parts (0.2 mol ofphthalic anhydride.

COMPARATIVE EXAMPLE 2

A resin solution R9 having a concentration of 47% and a viscosity of 51cp was prepared in the same manner as in Example 1, except for replacingthe hexahydrophthalic acid with 29.2 parts (0.2 mol) of adipic acid.

COMPARATIVE EXAMPLE 3

A resin solution R10 having a concentration of 49% and a viscosity of 46cp was prepared in the same manner as described in Example 5, exceptthat the carboxyl-terminated reaction product as prepared in Example 5was replaced with a carboxyl-terminated polyester obtained by reacting58.5 parts (0.4 mol) of adipic acid and 12.4 parts (0.2 mol) of ethyleneglycol at 160° to 180° C. for 3 hours and that the reaction with 40%glyoxal was continued for 3 hours.

EXAMPLE 8

In a four-necked flask equipped with a thermometer, a reflux condenserand a stirrer were charged 58.5 parts (0.4 mol) of triethylenetetramineand 12.0 parts (0.2 mol) of urea, and the mixture was heated at an innertemperature of 120° to 140° C. for 3 hours to effect deammoniation.Then, 34.4 parts (0.2 mol) of hexahydrophthalic acid was chargedtherein, and the mixture was heated at an inner temperature of 150° to160° C. for 5 hours to effect dehydrating amidation. After cooling to aninner temperature of 130° C., 48.0 parts (0.8 mol) of urea was added tothe reaction mixture, followed by allowing the mixture to react at atemperature of from 120° to 130° C. for 2 hours to effect deammoniation.The reaction mixture was cooled to 100° C., and water was added theretoto make a 50% aqueous solution. Then, 32.4 parts (0.4 mol) of 37%formalin was added to the solution. After adjusting to a pH of 5.1 with70% sulfuric acid, the mixture was allowed to react at 60° C. for 5hours. After cooling to 25° C., the reaction mixture was neutralized toa pH of 7.1 with a 28% sodium hydroxide aqueous solution to obtain aresin solution R11 having a concentration of 48.5% and a viscosity of 45cp.

EXAMPLE 9

In the same vessel as used in Example 8 were charged 58.5 parts (0.4mol) of triethylenetetramine and 12.0 parts (0.2 mol) of urea, and themixture was reacted at an inner temperature of 120° to 140° C. for 3hours to effect deammoniation. Thereafter, 30.4 parts (0.2 mol) oftetrahydrophthalic anhydride was charged therein, followed by heating atan inner temperature of 150° to 160° C. for 5 hours to effectdehydrating amidation. After cooling to 130° C., 48 parts (0.8 mol) ofurea was added to the reaction mixture, and the mixture was allowed toreact at 120° to 130° C. for 2 hours to effect deammoniation. Thereaction mixture was cooled to 100° C., and water was added thereto tomake a 50% aqueous solution. To the solution was added 32.4 parts (0.4mol) of 37% formalin, and the system was adjusted to a pH of 5.0 with70% sulfuric acid. The resulting mixture was allowed to react at 60° C.for 4 hours, followed by cooling to 25° C. Neutralization with a 28%sodium hydroxide aqueous solution gave a resin solution R12 having a pHof 7.34, a concentration of 49.0% and a viscosity of 52.1 cp.

EXAMPLE 10

In the same vassel as used in, Example 8, 75.7 parts (0.4 mol) oftetraethylenepentamine and 12.0 parts (0.2 mol) of urea were charged andheated at an inner temperature of 120° to 140° C. for 3 hours to effectdeammoniation. Then, 30.4 parts (0.2 mol) of tetrahydrophthalicanhydride was charged therein, and the mixture was heated at 150° to160° C. for 5 hours to effect dehydrating amidation. After cooling to aninner temperature of 130° C., 24.0 parts (0.4 mol) of urea was addedfollowed by deammoniation at 120° to 130° C. for 2 hours. After coolingto 100° C., water was added to the reaction mixture to make 50% aqueoussolution. To the solution was added 16.2 parts (0.2 mol) of 37% formalinfollowed by adjusting to a pH of 5.15 with 70% sulfuric acid. Themixture was allowed to react at 60° C. for 4 hours, cooled, andneutralized with a 28% sodium hydroxide aqueous solution to obtain aresin solution R13 having a pH of 7.23, a concentration of 49.5% and aviscosity of 79.5 cp.

EXAMPLE 11

In the same vessel as used in Example 8 were charged 58.5 parts (0.4mol) of triethylenetetramine and 12.0 parts (0.2 mol) of urea, and themixture was heated at an inner temperature of 120° to 140° C. for 3hours to effect deammoniation. Thereafter, 33.2 parts (0.2 mol) ofHN-2200 (the same as used in Example 2) was added thereto, followed byheating at an inner temperature of 150° to 160° C. for 5 hours to effectdehydrating amidation. After cooling to an inner temperature of 130° C.,12.0 parts (0.2 mol) of urea was added thereto, followed by allowing themixture to react at 120° to 130° C. for 2 hours to effect deammoniation.The reaction mixture was cooled to 100° C., and water was added theretoto make a 50% aqueous solution. To the solution was added 8.1 parts (0.1mol) of 37% formalin, and the system was adjusted to a pH of 5.0 with70% sulfuric acid. The mixture was heated to 60° C., at whichtemperature the system was allowed to react for 4 hours. The reactionmixture was cooled to 25° C. and then neutralized with a 28% sodiumhydroxide aqueous solution to obtain a resin solution R14 having a pH of7.06, a concentration of 50.1% and a viscosity of 52.0 cp.

EXAMPLE 12

In the same vessel as used in Example 8 were charged 12.4 parts (0.2mol) of ethylene glycol and 60.8 parts (0.4 mol) of tetrahydrophthalicanhydride, and the mixture was heated at 140° C. for 2 hours to obtain areaction product having a free carboxyl group. To the reaction mixturewas added 12.0 parts (0.2 mol) of urea, and 58.5 parts (0.4 mol) oftriethylenetetramine was further added thereto at 110° to 120° C. whilestirring. The mixture was subjected to deammoniation and dehydratingamidation by heating at 150° C. for 5 hours. After cooling to 130° C.,12.0 parts (0.2 mol) of urea was further added thereto, followed bydeammoniation at 120° to 130° C. for 2 hours. After cooling to 100° C.,water was added to the reaction mixture to make a 50% aqueous solution.Then, 8.1 parts (0.1 mol) of 37% formalin was added thereto, and thesystem was adjusted to a pH of 5.0 with 70% sulfuric acid. The mixturewas allow to react at 60° C. for 4 hours, and the resulting reactionmixture was cooled and neutralized with a 28% sodium hydroxide aqueoussolution to obtain a resin solution R15 having a pH of 7.23, aconcentration of 50.2% and a viscosity of 43 cp.

EXAMPLE 13

In the same vessel as used in Example 8 were charged 29.2 parts (0.2mol) of triethylenetetramine, and 30.8 parts (0.2 mol) ofhexahydrophthalic anhydride was added thereto, followed by heating to150° to 155° C., at which temperature dehydrating amidation waseffected. After the reaction mixture was cooled to 130° C., 12 parts(0.2 mol) of urea was added thereto, and deammoniation was carried outat 125° to 130° C. for 2 hours. After cooling to 60° C., water was addedto the reaction mixture to make a 50% aqueous solution. To the solutionwas added 8.1 parts (0.1 mol) of 37% formalin, and the mixture wasadjusted to a pH of 5.0 with 70% sulfuric acid, followed by allowing toreact at 60° to 65° C. for 4 hours.

After completion of the reaction, the reaction mixture was neutralizedwith a 28% sodium hydroxide aqueous solution to obtain a resin solutionR16 having a pH of 7.2, a concentration of 47.9% and a viscosity of 36cp.

EXAMPLE 14

In the same vessel as used in Example 8 were charged simultaneously 58.5parts (0.4 mol) of triethylenetetramine, 30.4 parts (0.2 mol) oftetrahydrophthalic anhydride and 12 parts (0.2 mol) of urea, and themixture was heated at 150° to 155° C. for 5 hours to effect dehydratingamidation and deammoniation simultaneously. After cooling to 130° C., 12parts (0.2 mol) of urea was additionally charged, and the mixture wasreacted at 125° to 130° C. for 2 hours for deammoniation. Water wasadded to the reaction mixture to make a 50% aqueous solution. To thesolution was added 8.1 parts (0.1 mol) of 37% formalin. After adjustingto a pH of 5.0 with 70% sulfuric acid, the mixture was allowed to reactat 60° to 65° C. for 4 hours, followed by cooling to 25° C. The reactionmixture was neutralized with a 28% sodium hydroxide aqueous solution toobtain a resin solution R17 having a pH of 7.42, a concentration of50.4% and a viscosity of 32 cp.

EXAMPLE 15

In the same vessel as used in Example 8, 58.5 parts (0.4 mol) oftriethylenetetramine and 12 parts (0.2 mol) of urea were charged, andthe mixture was heated at 145° to 150° C. for 4 hours to effectdeammoniation. Separately, 60.8 parts (0.4 mol) of tetrahydrophthalicanhydride and 15.2 parts (0.2 mol) of propylene glycol were mixed andheated at 140° to 150° C. for 2 hours to prepare a polyester. The wholequantity of the resulting polyester was transferred to the abovereaction vessel after completion of deammoniation, and the mixture washeated at an inner temperature of 150° to 155° C. for 4 hours to effectdehydration and deammoniation. After cooling to 130° C., 12 parts (0.2mol) of urea was added thereto, followed by deammoniation at 125° to130° C. for 2 hours. Water was added to the reaction mixture to make a50% aqueous solution. To the solution was added 8.1 parts (0.1 mol) of37% formalin, and the system was adjusted to a pH of 5.1 with 70%sulfuric acid. The mixture was allowed to react at 60° to 65° C. for 4hours. After cooling to 25° C., the reaction mixture was neutralizedwith a 28% sodium hydroxide aqueous solution to obtain a resin solutionR18 having a pH of 7.51, a concentration of 49.8% and a viscosity of 47cp.

COMPARATIVE EXAMPLE 4

A resin solution R19 having a pH of 7.2, a concentration of 48.7% and aviscosity of 44 cp was prepared in the same manner as in Example 8,except for replacing the hexahydrophthalic acid as used in Example 8with 29.6 parts (0.2 mol) of phthalic anhydride.

COMPARATIVE EXAMPLE 5

A resin solution R20 having a pH of 7.01, a concentration of 50.3% and aviscosity of 66 cp was prepared in the same manner as in Example 8,except for replacing the hexahydrophthalic acid as used in Example 8with 29.2 parts (0.2 mol) of adipic acid.

COMPARATIVE EXAMPLE 6

A resin solution R21 having a pH of 7.25, a concentration of 50.6% and aviscosity of 96 cp was prepared in the same manner as described inExample 12, except that the carboxyl-terminated polyester was obtainedby heating 58.5 parts (0.4 mol) of adipic acid and 12.4 parts (0.2 mol)of ethylene glycol at 160° to 180° C. for 3 hours and that the systemafter addition of 37% formalin was adjusted to a pH of 4.8.

EXAMPLE 16

In a four-necked flask equipped with a thermometer, a reflux condenserand a stirrer were charged 58.5 parts (0.4 mol) of triethylenetetramineand 12.0 parts (0.2 mol) of urea, and the mixture was heated at an innertemperature of 120° to 140° C. for 3 hours to effect deammoniation.Then, 34.4 parts (0.2 mol) of hexahydrophthalic acid was added thereto,followed by heating at an inner temperature of 150° to 160° C. for 5hours to effect dehydrating amidation. After cooling to an innertemperature of 130° C., 48.0 parts (0.8 mol) of urea was chargedtherein, and the mixture was allow to react at 120° to 130° C. for 2hours to effect deammoniation. The reaction mixture was cooled to 100°C. and diluted with water to make a 50% aqueous solution. To thesolution was added 18.5 parts (0.2 mol) epichlorohydrin, and the mixturewas allowed to react at 60° C. for 4 hours, followed by cooling to 25°C. The reaction mixture was adjusted to a pH of 7 with 35% hydrochloricacid, and water was added thereto to obtain a resin solution R22 havinga concentration of 50% and a viscosity of 52 cp.

EXAMPLE 17

In the same vessel as used in Example 16 was charged 29.2 parts (0.2mol) of triethylenetetramine, and 30.8 parts (0.2 mol) ofhexahydrophthalic anhydride was added thereto. The mixture was heated at150° to 155° C. to effect dehydrating amidation, followed by cooling to130° C. To the mixture was added 12 parts (0.2 mol) of urea, followed byallowing to react at 125° to 130° C. for 2 hours to effectdeammoniation. After cooling to 60° C., the reaction mixture was dilutedwith water to make a 50% aqueous solution. To the resulting solutionwere added 18.5 parts (0.2 mol) of epichlorohydrin and 15.4 parts (0.1mol) of diethyl sulfate, and the mixture was allowed to react at 60° C.for 7 hours, followed by cooling to 25° C. The reaction mixture wasadjusted to a pH of 6 with 20% sulfuric acid, and water was then addedthereto to obtain a resin solution R23 having a concentration of 50% anda viscosity of 63 cp.

EXAMPLE 18

In the same vessel as used in Example 16, 58.5 parts (0.4 mol) oftriethylenetetramine, 30.4 parts (0.2 mol) of tetrahydrophthalicanhydride and 12 parts (0.2 mol) of urea were charged simultaneously.The resulting mixture was heated at 150° to 155° C. for 5 hours toeffect dehydrating amidation and deammoniation at the same time. Aftercooling to 130° C., 12 parts (0.2 mol) of urea was added thereto,followed by allowing to react at 125° to 130° C. for 2 hours to effectdeammoniation. Water was added to the reaction mixture to make a 50%aqueous solution. To the solution was added 23.2 parts (0.4 mol) ofpropylene oxide, and the mixture was allowed to react at 25° C. for 6hours. Then, 9.3 parts (0.1 mol) of epichlorohydrin was added thereto,followed by heating at 60° C. for 3 hours. After cooling to 30° C., thereaction mixture was adjusted to a pH of 6 with 35% hydrochloric acid,and water was added thereto to prepare a resin solution R24 having aconcentration of 50% and a viscosity of 55 cp.

EXAMPLE 19

In the same vessel as used in Example 16 were charged 58.5 parts (0.4mol) of triethylenetetramine and 12 parts (0.2 mol) of urea, and themixture was reacted at 145° to 150° C. for 4 hours to effectdeammoniation. Separately, 60.8 parts (0.4 mol) of tetrahydrophthalicanhydride and 15.2 parts (0.2 mol) of propylene glycol were mixed andheated at 140° to 150° C. for 2 hours to prepare a polyester. The wholequantity of the resulting polyester was added to the above reactionvessel containing the deammoniation reaction mixture, and the resultingmixture was heated at an inner temperature of 150° to 155° C. for 4hours to effect dehydration and deammoniation. After cooling to 130° C.,12 parts (0.2 mol) of urea was added to the reaction mixture, followedby allowing to react at 125° to 130° C. for 2 hours to effectdeammoniation. Water was added to the reaction mixture to make a 50%aqueous solution. To the solution was added 18.5 parts (0.2 mol) ofepichlorohydrin, followed by allowing the mixture to react at 65° C. for2 hours. Then, 8.1 parts (0.1 mol) of 37% formalin was added thereto.After adjusting the system to a pH of 5 with 70% sulfuric acid, themixture was allowed to react at 65° C. for 4 hours, followed by coolingto 25° C. The reaction mixture was adjusted to a pH of 7 with a 28%sodium hydroxide aqueous solution to obtain a resin solution R25 havinga concentration of 50% and a viscosity of 48 cp.

EXAMPLE 20

In the same vessel as used in Example 16 were charged 12.4 parts (0.2mol) of ethylene glycol and 60.8 parts (0.4 mol) of tetrahydrophthalicanhydride, followed by heating at 140° C. for 2 hours to obtain areaction product having a free carboxyl group. To the reaction mixturewas added 12.0 parts (0.2 mol) of urea, and 58.5 parts (0.4 mol) oftriethylenetetramine was further added thereto at 110° to 120° C. whilestirring. The mixture was then heated at 150° C. for 5 hours to effectdeammoniation and dehydrating amidation. After cooling to 130° C., 12.0parts (0.2 mol) of urea was added to the reaction mixture, followed byallowing the mixture to react at 120° to 130° C. for 2 hours to effectdeammoniation. The reaction mixture was cooled to 100° C., and water wasadded thereto to make a 50% aqueous solution. Then, 77 parts (0.5 mol)of diethyl sulfate was charged therein, and the mixture was reacted at60° C. for 4 hours, followed by cooling to 25° C. The system wasadjusted to a pH of 7 with 20% sulfuric acid, and water was addedthereto to obtain a resin solution R26 having a concentration of 50% anda viscosity of 43 cp.

EXAMPLE 21

The same procedure as described in Example 19 was repeated except that14.5 parts (0.1 mol) of 40% glyoxal was used in place of the 37%formalin as used in Example 19 and, after adjusting to a pH of 6 with70% sulfuric acid, the resulting mixture was reacted at 55° C. for 4hours. There was obtained a resin solution R27 having a concentration of50% and a viscosity of 51 cp.

COMPARATIVE EXAMPLE 7

A resin solution R28 having a concentration of 50% and a viscosity of 49cp was prepared in the same manner as described in Example 16, exceptfor using 29.6 parts (0.2 mol) of phthalic anhydride in place of thehexahydrophthalic acid as used in Example 16.

COMPARATIVE EXAMPLE 8

A resin solution R29 having a concentration of 50% and a viscosity of 58cp was prepared in the same manner as described in Example 16, exceptfor using 29.2 parts (0.2 mol) of adipic acid in place of thehexahydrophthalic acid as used in Example 16.

COMPARATIVE EXAMPLE 9

A resin solution R30 having a concentration of 50% and a viscosity of 57cp was prepared in the same manner as in Example 20, except that thecarboxyl-terminated polyester was obtained by heating 58.5 parts (0.4mol) of adipic acid and 12.4 parts (0.2 mol) of ethylene glycol at 160°to 180° C. for 3 hours.

EXAMPLES 22 TO 28 AND COMPARATIVE EXAMPLES 10 TO 13

A paper coating composition was prepared by using each of the resinsolutions R1 to R10 as obtained in Examples 1 to 7 and ComparativeExample 1 to 3 and Sumirez® resin 613 (a trade name for a water-solublemelamine-formaldehyde resin produced by Sumitomo Chemical Co., Ltd.)according to the formulation as shown in Table 1 below:

                  TABLE 1                                                         ______________________________________                                                        Compounding                                                                   Ratio                                                                         (part)*.sup.6                                                 ______________________________________                                        Pigment                                                                       Ultrawhite ® 90*.sup.1                                                                      75                                                          Carbital ® 90*.sup.2                                                                        25                                                          Dispersing                                                                    Agent                                                                         Sumirez ® resin DS-10*.sup.3                                                                0.2                                                         Aqueous                                                                       Binder                                                                        SN-307*.sup.4     12                                                          Oji Ace ® A*.sup.5                                                                          6                                                           Resin                                                                         see Table 2       0.3                                                         ______________________________________                                         Note:                                                                         *.sup.1 Clay manufactured by Engel Hard Minerals Inc., U.S.A.                 *.sup.2 Calcium carbonate manufactured by Fuji Kaolin Co., Ltd.               *.sup.3 Polyacrylic acid type pigment dispersant produced by Sumitomo         Chemical Co., Ltd.                                                            *.sup.4 Styrenebutadiene latex produced by Sumitommo Naugatuc Co., Ltd.       *.sup.5 Oxidized starch produced by Oji International Starch Co., Ltd.        *.sup.6 On a solids content basis                                        

Each of the thus prepared compositions was adjusted so as to have atotal solids content of 60% and a pH of about 8.5 by addition of waterand a 10% sodium hydroxide aqueous solution. The coating composition wascoated with a wire rod on one side of fine paper having a basis weightof 80 g/m² at a spread of about 14 g/m², immediately followed by dryingin hot air at 120° C. for 30 seconds. After moisture-conditioning at 20°C. and 65% RH (relative humidity) for 16 hours, the coated paper wassubjected to supercalendering twice under conditions of 60° C. intemperature and 60 kg/cm in linear pressure.

Each of the resulting coated papers was evaluated for water resistance,ink receptivity and evolution of formaldehyde in accordance with thefollowing test methods. The results obtained are shown in Table 2.

Water Resistance (a) Wet Rub Method (WR)

About 0.1 ml of ion-exchange water was dropped on the coated surface,and 7 rubs with a finger tip were given. The matter rubbed off wastransferred to black paper, and its amount was visually determined toevaluate water resistance based on five ratings of from 1 (poor) to 5(excellent).

(b) Wet Pick Method (WP)

The coated surface was wetted with a water-supply roll by means of an RItester (manufactured by Akira Seisakusho Co., Ltd.), and printed. Thepicking was visually observed to evaluate water resistance based on fiveratings of from 1 (poor) to 5 (excellent).

Ink Receptivity Method A

The coated surface was wetted with a water-supply roll by means of an RItester, and printed. Ink receptivity was evaluated based on five ratingsof from 1 (poor) to 5 (excellent).

Method B

Printing was carried out while incorporating water in an ink by the useof an RI tester. Evaluation of ink receptivity was made based on thesame ratings as adopted in Method A.

Evolution of Formaldehyde

A sample weighting 25 g was quantitatively analyzed for formaldehyde inaccordance with JIS-L1041-1976 "Liquid Phase Extraction Method (2),Acetylacetone Method (Method A)".

EXAMPLES 29 TO 36 AND COMPARATIVE EXAMPLES 14 TO 17

Paper coating compositions were prepared in the same manner as inExamples 22 to 28 and Comparative Examples 10 to 13, except for usingresin solutions R11 to R21 in place of R1 to R10. The test resultsobtained are shown in Table 3.

EXAMPLE 37 TO 42 AND COMPARATIVE EXAMPLES 18 TO 21

Paper coating compositions were prepared in the same manner as inExamples 22 to 28 and Comparative Examples 10 to 13, except for usingresin solutions R22 to R30 in place of R1 to R10. The test resultsobtained are shown in Table 4.

                                      TABLE 2                                     __________________________________________________________________________                                             Com. Com.                                                                              Com.                                                                              Com.                               Ex. Ex.  Ex. Ex. Ex.  Ex. Ex. Ex.  Ex. Ex. Ex.                                22  23   24  25  26   27  28  10   11  12  13   Blank              __________________________________________________________________________    Coating Composition                                                           Resin Used  R1  R2   R3  R4  R5   R6  R7  R8   R9  R10                                                                               613**                                                                              none              pH (at 25° C.)                                                                      8.4                                                                               8.4                                                                                8.5                                                                               8.4                                                                               8.5                                                                                8.4                                                                               8.5                                                                               8.6                                                                                8.5                                                                               8.6                                                                               8.5                                                                                8.5              Viscosity (at 25° C.)*                                                            1150                                                                              1140 1160                                                                              1130                                                                              1140 1130                                                                              1110                                                                              1170 1310                                                                              1420                                                                              1180 1150               (cp)                                                                          Coated Paper                                                                  Water Resistance:                                                             WR Method    4.8                                                                               4.8                                                                                4.8                                                                               4.8                                                                               4.8                                                                                4.8                                                                               4.8                                                                               3.0                                                                                2.5                                                                               2.5                                                                               2.5                                                                                1.0              WP Method    4.6                                                                               4.5                                                                                4.6                                                                               4.8                                                                               4.6                                                                                4.7                                                                               4.5                                                                               2.5                                                                                2.4                                                                               2.2                                                                               2.0                                                                                1.0              Ink Receptivity:                                                              Method A     4.8                                                                               4.6                                                                                4.6                                                                               4.7                                                                               4.8                                                                                4.7                                                                               4.7                                                                               2.8                                                                                2.5                                                                               2.8                                                                               1.5                                                                                1.0              Method B     4.7                                                                               4.8                                                                                4.7                                                                               4.7                                                                               4.6                                                                                4.6                                                                               4.6                                                                               3.0                                                                                2.4                                                                               2.5                                                                               1.5                                                                                1.0              Amount of Evolved                                                                          0   0    0   0   0    2   1   0    0   0  34    1                Formaldehyde (ppm)                                                            Spread (g/m.sup.2)                                                                        14.6                                                                              14.5                                                                               14.5                                                                              14.6                                                                              14.8                                                                               14.5                                                                              14.7                                                                              14.6                                                                               14.8                                                                              14.5                                                                              14.5                                                                               14.5              __________________________________________________________________________     Note:                                                                         *Determined by the use of a Brookfield viscometer at 60 rpm (hereinafter      the same)                                                                     **Sumirez ® resin 613 (hereinafter the same).                        

                                      TABLE 3                                     __________________________________________________________________________                                               Com.                                                                              Com.                                                                              Com.                                                                              Com.                              Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex.                               29  30  31  32  33  34  35  36  14  15  16  17  Blank              __________________________________________________________________________    Coating Composition                                                           Resin Used  R11                                                                               R12                                                                               R13                                                                               R14                                                                               R15                                                                               R16                                                                               R17                                                                               R18                                                                               R19                                                                               R20                                                                               R21                                                                               613**                                                                             none              pH (at 25° C.)                                                                      8.4                                                                               8.4                                                                               8.5                                                                               8.4                                                                               8.5                                                                               8.4                                                                               8.5                                                                               8.5                                                                               8.6                                                                               8.5                                                                               8.6                                                                               8.5                                                                               8.5              Viscosity (at 25° C.)*                                                            1160                                                                              1148                                                                              1150                                                                              1128                                                                              1142                                                                              1120                                                                              1130                                                                              1190                                                                              1180                                                                              1330                                                                              1470                                                                              1180                                                                              1148               (cp)                                                                          Coated Paper                                                                  Water Resistance:                                                             WR Method    4.8                                                                               4.8                                                                               4.8                                                                               4.8                                                                               4.8                                                                               4.8                                                                               4.8                                                                               4.8                                                                               3.0                                                                               2.5                                                                               2.5                                                                               2.5                                                                               1.0              WP Method    4.4                                                                               4.5                                                                               4.4                                                                               4.8                                                                               4.8                                                                               4.7                                                                               4.7                                                                               4.8                                                                               2.5                                                                               2.2                                                                               2.6                                                                               2.0                                                                               1.0              Ink Receptivity:                                                              Method A     4.8                                                                               4.5                                                                               4.6                                                                               4.8                                                                               4.8                                                                               4.8                                                                               4.7                                                                               4.8                                                                               3.0                                                                               2.5                                                                               2.8                                                                               1.5                                                                               1.0              Method B     4.6                                                                               4.8                                                                               4.6                                                                               4.7                                                                               4.5                                                                               4.6                                                                               4.7                                                                               4.6                                                                               3.0                                                                               2.5                                                                               2.5                                                                               1.5                                                                               1.0              Amount of Evolved                                                                          3   2   2   2   2   2   2   2   3   3   3  32   1                Formaldehyde (ppm)                                                            Spread (g/m.sup.2)                                                                        14.3                                                                               14.6                                                                             14.5                                                                              14.5                                                                              14.3                                                                              14.4                                                                              14.7                                                                              14.2                                                                              14.2                                                                              14.8                                                                              14.5                                                                              14.6                                                                              14.2              __________________________________________________________________________

                                      TABLE 4                                     __________________________________________________________________________                                       Com.                                                                              Com.                                                                              Com.                                                                              Com.                                      Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex.                                       37  38  39  40  41  42  18  19  20  21  Blank                      __________________________________________________________________________    Coating Composition                                                           Resin Used  R22                                                                               R23                                                                               R24                                                                               R25                                                                               R26                                                                               R27                                                                               R28                                                                               R29                                                                               R30                                                                               613**                                                                             none                      pH (at 25° C.)                                                                      8.4                                                                               8.4                                                                               8.5                                                                               8.4                                                                               8.5                                                                               8.4                                                                               8.6                                                                               8.5                                                                               8.6                                                                               8.5                                                                               8.5                      Viscosity (at 25° C.)*                                                            1145                                                                              1150                                                                              1130                                                                              1140                                                                              1110                                                                              1150                                                                              1150                                                                              1310                                                                              1360                                                                              1170                                                                              1130                       (cp)                                                                          Coated Paper                                                                  Water Resistance:                                                             WR Method    4.8                                                                               4.8                                                                               4.8                                                                               4.8                                                                               4.8                                                                               4.8                                                                               3.0                                                                               2.5                                                                               2.5                                                                               2.5                                                                               1.0                      WP Method    4.5                                                                                4.5                                                                              4.7                                                                               4.6                                                                               4.8                                                                               4.7                                                                               2.4                                                                               2.4                                                                               2.5                                                                               2.0                                                                               1.0                      Ink Receptivity:                                                              Method A     4.8                                                                               4.6                                                                               4.5                                                                               4.8                                                                               4.7                                                                               4.8                                                                               3.0                                                                               2.6                                                                               2.6                                                                               1.5                                                                               1.0                      Method B     4.7                                                                               4.8                                                                               4.6                                                                               4.6                                                                               4.5                                                                               4.6                                                                               2.8                                                                               2.5                                                                               2.5                                                                               1.5                                                                               1.0                      Amount of Evolved                                                                          0   0   0   1   0   0   0   0   0  35   1                        Formaldehyde (ppm)                                                            Spread (g/m.sup.2)                                                                        14.8                                                                              14.6                                                                              14.5                                                                              14.5                                                                              14.3                                                                              14.4                                                                              14.8                                                                              14.6                                                                              14.5                                                                              14.5                                                                              14.3                      __________________________________________________________________________

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A process for producing a resin, which comprisesreacting (a) a polyalkylenepolyamine, (b) an alicyclic dibasiccarboxylic acid and/or a reaction product having a free carboxyl groupthat is obtained by reacting an alicyclic dibasic carboxylic acid with aglycol having two carboxyl groups directly attached to the acyclic ring,wherein the carboxyl groups in the alicyclic dibasic carboxylic acid areconnected directly with the alicyclic ring, (c) a urea, and (d) analkehyde and/or an alkylating agent selected from compounds representedby the formula:

    R.sub.1 --X

wherein R₁ represents a lower alkyl group, an alkenyl group, a benzylgroup or a phenoxyethyl group; and X represents a halogen atom;compounds represented by the formula:

    (R.sub.2 O).sub.2 SO.sub.v

wherein R₂ represents a lower alkyl group, and v represents 1 or 2;compounds represented by formula: ##STR5## wherein R₃ represents ahydrogen atom, a lower alkyl group, a hydroxyalkyl group or a phenylgroup; compounds represented by formula: ##STR6## wherein X represents ahalogen atom, and w represents 1, 2 or 3, compounds represented byformula:

    HOCH.sub.2 (CH.sub.2).sub.w X

wherein X and w are as defined above, compounds represented by formula;##STR7## wherein X is as defined above; and either one of Y and Zrepresents a halogen atom, with the another representing a hydroxylgroup, and mixtures thereof.
 2. A process as in claim 1, wherein saidaldehyde is selected from formaldehyde, glyoxal and a mixture thereof.3. A process as in claim 1, wherein said alkylating agent isepichlorohydrin.
 4. A process as in claim 1, wherein said dibasiccarboxylic acid is in the form of an ester or anhydride thereof.
 5. Aprocess as in claim 1, wherein said alicyclic dibasic carboxylic acid ischosen from the group consisting of tetrahydrophthalic acid,hexahydrophthalic acid, cyclohexane-1,4-dicarboxylic acid,4-methyltetrahydrophthalic acid, 4-methylhexahydrophthalic acid or 1:2adduct of a styrene and maleic acid.
 6. A process as in claim 1, whereinsaid alicyclic dibasic carboxylic acid is hexahydrophthalic acid,tetrahydrophthalic acid or methyltetrahydrophthalic acid.